CN102608823A - Optical device, analyzing apparatus and spectroscopic method - Google Patents
Optical device, analyzing apparatus and spectroscopic method Download PDFInfo
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- CN102608823A CN102608823A CN2011101076983A CN201110107698A CN102608823A CN 102608823 A CN102608823 A CN 102608823A CN 2011101076983 A CN2011101076983 A CN 2011101076983A CN 201110107698 A CN201110107698 A CN 201110107698A CN 102608823 A CN102608823 A CN 102608823A
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- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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Abstract
An optical device includes a first projection group in which electric conductor projections are arranged at a first period along a direction parallel to a virtual plane. When light traveling in a direction inclined with respect to a vertical line directed to the virtual plane is incident on the first projection group, surface plasmon resonance is generated at a first resonance peak wavelength and a second resonance peak wavelength. A first resonance peak wavelength band including the first resonance peak wavelength includes an excitation wavelength in surface-enhanced Raman scattering. A second resonance peak wavelength band including the second resonance peak wavelength includes a Raman scattering wavelength in the surface-enhanced Raman scattering.
Description
Technical field
The present invention relates to optical device, analytical equipment and light-splitting method etc.
Background technology
In recent years, the demand of the employed sensors such as detection of medical diagnosis or diet is increasing, thereby thirsts for exploitation high sensitivity and small-sized sensor.In order to satisfy such requirement, discussing with electrochemical method is various types of sensors of representative.Wherein, according to integrability, low cost, do not select to measure reasons such as environment, more and more tend to use the sensor of surface plasma body resonant vibration.
For example, in patent documentation 1, disclose utilization is improved transducer sensitivity by the local surface plasma resonance of the substrate that is fixed with metal particle from the teeth outwards method.
Patent documentation 1: TOHKEMY 2000-356587 communique
Patent documentation 2: TOHKEMY 2007-10648 communique
Patent documentation 3: TOHKEMY 2009-250951 communique
Utilizing the electric field that causes by surface plasma body resonant vibration to strengthen the intensity of Raman scattering; And under the sensitivity that makes the sensing detection of the object situation about improving, its electric field enhancing degree decides through the product of electric field enhancing degree in the excitation wavelength and the electric field enhancing degree in the Raman scattering wavelength.Thereby, for the high sensitivityization of sensing detection, electric field enhancing degree and the electric field enhancing degree in the Raman scattering wavelength in the excitation wavelength are improved simultaneously.
For example, in the method for above-mentioned patent documentation 1,, so in resonant wavelength, also produce fluctuation is arranged, thereby the amplitude of extinction spectrum (absorbance spectrum) broadens owing to be difficult to make the size of metal particle and arrangement impartial.In addition, also a generation has a resonance peak.Therefore, for example, in the purposes of the thin object of sensing detection, cause being difficult in excitation wavelength and this two wavelength of Raman scattering wavelength, obtaining sufficient electric field enhancing degree.
In addition, in patent documentation 2, disclose to have and carry out the resonance peak of displacement and carry out the technology of local plasmon resonance body sensor of the resonance peak of displacement at short wavelength side at long wavelength side.In addition, in patent documentation 3, disclose for can with a plurality of wavelength resonances, constitute the technology of the electric field enhance device of small resonator through a plurality of resonance zones.
Summary of the invention
According to several embodiments of the present invention, the electric field enhancing degree that can improve in the excitation wavelength and optical device, analytical equipment and the light-splitting method etc. of the electric field enhancing degree in the Raman scattering wavelength can be provided.
The said optical device of the optical device that first aspect present invention relates to has: the first projection crowd; The said first projection crowd arranges with the period 1 through the direction that the projection edge of electric conductor is parallel with imaginary plane and forms; Wherein, Surface plasma body resonant vibration making light be incident to the said first projection group time of arranging with the said period 1 produces at the first resonance peak wavelength and the second resonance peak wavelength respectively; The said light that only advances along the direction that tilts with respect to vertical line towards said imaginary plane; The first resonance peak wave band that comprises the said first resonance peak wavelength comprises the excitation wavelength lambda 1 in the SERS, and the second resonance peak wave band that comprises the said second resonance peak wavelength comprises the Raman scattering wavelength X 2 in the said SERS.
According to a first aspect of the invention, the projection edge of the first projection crowd's the electric conductor direction parallel with imaginary plane arranged with the period 1.Go into the light that direction that directive tilts with respect to the vertical line towards imaginary plane is advanced the first projection crowd who arranges with this period 1.Through the light of this incident, in the first resonance peak wavelength and the second resonance peak wavelength, producing respectively has surface plasma body resonant vibration.At this moment; In comprising the first resonance peak wave band of the first resonance peak wavelength, to comprise the excitation wavelength lambda 1 in the SERS; The mode that in comprising the second resonance peak wave band of the second resonance peak wavelength, comprises the Raman scattering wavelength X 2 in the SERS, the incident angle of setting period 1 and light.Through like this, can improve electric field enhancing degree and the electric field enhancing degree in the Raman scattering wavelength in the excitation wavelength etc.
In addition, in second aspect of the present invention, said Raman scattering wavelength X 2 can be to be longer than the wavelength of said excitation wavelength lambda 1.
In view of the above, can use the long Raman scattering wavelength X 2 of ripple of comparing with excitation wavelength lambda 1 in Raman diffused light to detect object.
In addition, in the third aspect of the invention, can rectilinearly polarized light be arranged incident as said incident light, composition parallel with said imaginary plane on the polarization direction of said rectilinearly polarized light and the said first projection crowd's orientation parallel.
In view of the above, can be to optical device incident rectilinearly polarized light, composition parallel with imaginary plane on the direction of polarized light of this rectilinearly polarized light and the first projection crowd's orientation parallel.Through like this, can excite the propagation surface plasma.
In addition, in fourth aspect of the present invention, can comprise the second projection crowd who is formed by electric conductor at the said first projection crowd's end face, can the edge parallel with the said imaginary plane direction of the said second projection crowd is to arrange the second round that is shorter than the said period 1.
In view of the above, direction that can the second projection crowd is parallel with imaginary plane in the first projection crowd's end face upper edge is to arrange second round.Through like this, can on the second projection crowd, excite local surface plasma.
In addition; In aspect the of the present invention the 5th; Can comprise the 3rd projection crowd who is formed by electric conductor at the face that is arranged with the said first projection crowd and be positioned between the said first projection crowd's abutment lug, said the 3rd projection crowd can the edge direction parallel with said imaginary plane arrange with the period 3 that is shorter than the said period 1.
In view of the above, can the edge direction parallel the 3rd projection crowd be arranged on the face between the abutment lug that is arranged with the said first projection crowd and is positioned at the first projection crowd with the period 3 with imaginary plane.Through like this, can in the 3rd projection crowd, excite local surface plasma.
In addition, the present invention relates to a kind of analytical equipment on the other hand, and it comprises: light source; The described optical device in above-mentioned arbitrary aspect; First optical system makes from the incident light of the said wavelength X 1 of said light source to tilt with respect to the vertical line towards the said imaginary plane of said optical device and be incident to said electric conductor grating; Second optical system is extracted Raman diffused light from the light of said electric conductor grating scattering through said optical device or reflection; And detecting device, detect the said Raman diffused light that receives (receiving light) through said second optical system.
In addition; In aspect the of the present invention the 7th; Said first optical system can depart from the optical axis ground incident of said first optical system through making said incident light, thereby makes said incident light with respect to tilting towards the vertical line of said imaginary plane and being incident to said electric conductor grating.
In addition; In eight aspect of the present invention; Said analytical equipment can also comprise: the support portion makes towards the vertical line of the said imaginary plane of the said optical device inclined light shaft with respect to said first optical system, and supports said optical device; Said first optical system is through making said incident light with the mode incident consistent with the optical axis of said first optical system, thereby said incident light is tilted with respect to the vertical line towards said imaginary plane and is incident to said electric conductor grating.
In addition, nineth aspect present invention relates to a kind of light-splitting method, comprising: prepare the first projection crowd, the said first projection crowd arranges with the period 1 through the direction that the projection edge of electric conductor is parallel with imaginary plane and forms; Make light be incident to the said first projection crowd who arranges with the said period 1, the said light that only advances along the direction that tilts with respect to vertical line towards said imaginary plane; And produce surface plasma body resonant vibration at the first resonance peak wavelength and the second resonance peak wavelength respectively; Wherein, The first resonance peak wave band that comprises the said first resonance peak wavelength comprises the excitation wavelength lambda 1 in the SERS, and the second resonance peak wave band that comprises the said second resonance peak wavelength comprises the Raman scattering wavelength X 2 in the said SERS.
Description of drawings
Fig. 1 is the key diagram of the comparative example of present embodiment.
Fig. 2 is the key diagram of the comparative example of present embodiment.
Fig. 3 is the key diagram of the comparative example of present embodiment.
(A) of Fig. 4 is the key diagram of Raman scattering beam split ratio juris, and (B) of Fig. 4 is the example of the Raman spectrum obtained through the Raman scattering beam split.
Fig. 5 is the key diagram of the method for present embodiment.
Fig. 6 is the routine stereographic map of formation of the sensor chip of present embodiment.
Fig. 7 is the sectional view of the sensor chip of present embodiment.
Fig. 8 is the characteristic example of the intensity of reflected light of sensor chip.
Fig. 9 is the key diagram of the establishing method of two resonance peak wavelength.
Figure 10 is the characteristic example of intensity of reflected light of the variation of sensor chip.
Figure 11 is the stereographic map that second of sensor chip constitutes example.
Figure 12 is the sectional view that second of sensor chip constitutes example.
Figure 13 is the formation example of analytical equipment.
Figure 14 is the key diagram that is used to make first method of incident light oblique incidence.
Figure 15 is the key diagram that is used to make second method of incident light oblique incidence.
Embodiment
Below, to a preferred embodiment of the present invention will be described in detail.In addition, following illustrated example is not the unreasonable qualification to the content of being put down in writing in protection scope of the present invention of the present invention, and whole formations of explaining among the embodiment may not all be essential features of the present invention.
1. comparative example
Referring to figs. 1 through Fig. 3, to the comparative example as present embodiment, the situation that will be used for the SERS beam split by the local plasmon resonance body that metal particle causes describes.At first, with reference to Fig. 1 and Fig. 2, the local surface plasma resonance that is caused by metal particle is described.
As stated, as used high sensitivity such as medical diagnosis and small-sized sensor, more and more tend to use surface plasma body resonant vibration (SPR:Surface Plasmon Resonance: sensor surface plasma body resonant vibration).This sensor is used for through exciting light excitating surface plasma (SP:Surface Plasmon: surface plasma), and utilize the variation of the absorbance of its surface plasma body resonant vibration to come sensing detection attached to the object on the metal surface on the metal surface.Here, so-called surface plasma body resonant vibration is meant because of the intrinsic boundary condition in interface and causes the vibration mode with the electronics dilatational wave of optically-coupled.
As the method that excites this surface plasma, the known method that employing surface relief gratings or prism are arranged.For example, as the sensor of having used surface plasma body resonant vibration, there is the method that adopts total reflection prism.In the method, form metal film on the surface of total reflection prism, and object is contacted with its metal film.And through to total reflection prism incident exciting light, the interface between air and metal film excites the propagation surface plasma, and detects according to the variation of the absorbance that causes because of its propagation surface plasma and to have or not the absorption object.Conducts such as use antigen-antibody reaction make the method for object absorption.
In addition, as the additive method of excitating surface plasma, exist to excite local surface plasma (the LSP:Localized Surface Plasmon: method local surface plasma) that causes by metal particle.In this local surface plasma, excited surface plasma local is on the microstructure that substrate surface forms, and the surface plasma through its local brings out the electric field of remarkable enhancing.It is purpose that motion has to utilize such enhancing electric field to improve transducer sensitivity, utilizes local surface plasma resonance (the LSPR:Localized Surface Plasmon Resonance: sensor local surface plasma resonance) that has adopted metal particle or metal nano structure.
For example, as such sensor, there is the method for above-mentioned patent documentation 1.As shown in Figure 1, in the method, fixing metal particulate 20 on the surface of transparency carrier 10 to these transparency carrier 10 irradiation incident lights, thereby is measured the catoptrical absorbance that has seen through metal particle 20.As shown in Figure 2, when on metal particle 20, being attached with object, be changed to the absorption spectrum shown in A2 from the absorption spectrum shown in the A1.In the method for patent documentation 1, the variation through this absorbance detects near the variation of the medium the metal particle, and detects the absorption or the accumulation of object.
But, in the method, be difficult to make equably size and shape and regular the metal particle of arranging of metal particle.When the size that can not control metal particle and arrangement, the absorption and the resonant wavelength that are produced by plasma resonance have also produced fluctuation.Therefore, as shown in Figure 2, the amplitude of absorption spectrum broadens, and causes peak strength to descend.And if peak strength descends, the signal that then detects near the variation of the medium of metal particle diminishes, thereby in making the transducer sensitivity raising, also produces boundary.Therefore, in the purposes according to the absorption spectrum designated substance, it is not enough that the sensitivity of sensor becomes.
So,, consider to have the sensor is applied to SERS (SERS:Surface Enhanced Raman Scattering: method SERS) as the sensitivity of method that improves sensor.This method is through strengthening Raman diffused light according to surface plasma body resonant vibration, thereby improves the sensitivity of method of Raman spectrum.
But, in the method, because gain in strength so need in two wavelength, improve electric field (following formula (1)) that transducer sensitivity is gained in strength and decided according to the electric field in excitation wavelength (λ 1 shown in Fig. 4 (A)) and Raman scattering wavelength (λ 2).
For example, in existing SERS sensor, owing to only utilize a resonance peak, so must make the wavelength of resonance peak and which consistent wavelength in excitation wavelength or the Raman scattering wavelength.At this moment, can only utilize the electric filed enhanced effect in which the scattering process of wavelength, thereby can not expect high electric filed enhanced effect.
In addition, be applicable to that with sensor the situation of SERS is an example with above-mentioned patent documentation 1.At this moment, in Fig. 2, as stated, and owing to only have the surface plasma body resonant vibration peak value of a broadness, thus need be with respect to excitation wavelength and Raman scattering wavelength, with the set positions of resonance peak in position.That is to say that this is because its resonance peak wavelength is given bigger influence to the enhancing degree of local electric field.Specifically, as shown in Figure 3, with respect to Raman shift, can obtain broader resonance peak.Therefore, as with the resonance peak wavelength set between excitation wavelength and Raman scattering wavelength, then can expect electric filed enhanced effect through these two processes of excitation process and Raman scattering process.But, because resonance peak is broad, thus the weakened that in each process, resonates, thus the enhancing degree of talkative whole process is not sufficient.
2. the method for present embodiment
Thereby, in the present embodiment,, make to produce two resonance peaks, and its two resonance peaks are set at excitation wavelength and Raman scattering wavelength through to metal grating incident incident light obliquely as an example of electric conductor grating, thus the raising transducer sensitivity.Below, the method for this present embodiment is described.At first, the employed Raman scattering optical spectroscopy of present embodiment is described.
Fig. 4 (A) illustrates the key diagram of Raman scattering beam split ratio juris.Shown in Fig. 4 (A), when to the light Lin of the single wavelength of target molecule X (object) irradiation, in scattered light, produce the Raman diffused light Ram that has with the wavelength X in different wavelengths λ 2 of incident light Lin.Energy difference between this Raman diffused light Ram and the incident light Lin is corresponding with the energy of vibrational energy level, rotational energy level and the electron level of target molecule X.Target molecule X is owing to have a distinctive vibrational energy corresponding with its structure, thus the light Lin through the single wavelength of use, thus can the intended target molecule.
For example, when with the vibrational energy of incident light Lin as V1, the vibrational energy of target molecule X as V2, during as V3, is become V3=V1-V2 with the vibrational energy of Raman diffused light Ram.That is to say, because V3 becomes the vibrational energy based on V2, thus pass through to measure the wavelength X 2 of Raman diffused light Ram, thus can intended target molecule X.
In addition, even after the major part of incident light Lin and target molecule X have collided, also have with collide before the energy of identical size.Should be called Rayleigh scattering light Ray by flexible scattered light.When such as with the vibrational energy of Rayleigh scattering light Ray during as V4, V4=V1 then.That is to say that the wavelength X 1 of Rayleigh scattering light Ray is λ 1=λ in.
Fig. 4 (B) illustrates the example of the Raman spectrum of obtaining through the Raman scattering beam split (relation between Raman shift and the Raman scattering intensity).The transverse axis of the curve map shown in Fig. 4 (B) illustrates Raman shift.Raman shift is exactly wave number poor of wave number (vibration number) and the incident light Lin of Raman diffused light Ram, and is at target molecule X and obtains distinctive value under the molecular link state.
Shown in Fig. 4 (B), when the scattering strength with the scattering strength (spectrum peak) of the Raman diffused light Ram shown in the B1 and the Rayleigh scattering light Ray shown in the B2 compares, can know that Raman diffused light Ram is faint.Like this, the Raman scattering optical spectroscopy is that the recognition capability of target molecule X is remarkable, and the low assay method of sensitivity of sensing detection target molecule X itself.Therefore, in the present embodiment, the optical spectroscopy of use SERS is realized the high sensitivityization of sensor.
In order to realize using the highly sensitive surface plasma resonance sensor of this SERS, the enhancing degree of preferred local electric field (below, suitably economize slightly enhancing degree) big as far as possible.Enhancing degree α is with following formula (1) expression (M.lnoue, K.ohtaka, J.phys.Soc.Jpn., 52,3853 (1983)).Here, α ray is the excitation wavelength enhancing degree of (equating with the Rayleigh scattering wavelength), and α ram is the enhancing degree of Raman scattering wavelength.
α＝αray×αram (1)
According to following formula (1), in the enhancing degree that improves the SERS process, need improve enhancing degree and these two enhancing degree of the enhancing degree in the Raman scattering process in the excitation process simultaneously.Therefore, as shown in Figure 5 in the present embodiment, near two strong resonance peaks of generation excitation wavelength and Raman scattering wavelength only.Through like this,, thereby can significantly improve the reinforced effects of local electric field according to the effect that multiplies each other of two scattering processes.
3. constitute example
With reference to Fig. 6 to Fig. 9, near the formation example of the present embodiment of two resonance peaks of generation excitation wavelength and Raman scattering wavelength is described.In addition, below since with each inscape as the size that on accompanying drawing, can discern degree, so that the size of each inscape and ratio are suitably different with the size and the ratio of reality.
Fig. 6 is the routine stereographic map of formation of the sensor chip (optical device, electric conductor grating) of present embodiment.This sensor chip is to utilize surface plasma body resonant vibration and SERS to detect the chip of object (target substance, target molecule) usefulness, and it comprises base material 100 (substrate), the first projection crowd 110.This sensor chip is to have the periodic metal grating of one dimension.
In addition, below, though be that the situation of the metal grating that forms with metal describes with sensor chip, be not limited thereto in the present embodiment.That is to say, sensor chip so long as the grating that forms by electric conductor get final product, such as also being the grating that forms by semiconductor (for example polysilicon).
Specifically, base material 100 comprises Ag (silver) or Au metals (sensu lato electric conductor) such as (gold), for example, forms quadrangle or circular tabular.The first projection crowd 110 goes up by the cycle configuration at the first direction D1 along the plane (sensu lato face) of base material 100, and such as by forming with base material 100 same metal.Here, the plane of base material 100 is such as being the surface 120 at the base material 100 that is formed with the first projection crowd, 110 sides.
More particularly, the cross sectional shape of each projection of the first projection crowd 110 on the orientation D1 of projection begins to form convex form from the surface 120 of base material 100.Convex form is rectangle, trapezoidal or arc etc.For example, as shown in Figure 6, observe from the vertical view of overlooking base material 100, the first projection crowd 110 forms the parallel striated of second direction D2 with direction D1 quadrature.
Fig. 7 illustrates the sectional view of the sensor chip of present embodiment.The cross section of this sectional view is the face vertical with the plane of base material 100, and it is the parallel face of orientation D1 with the first projection crowd 110.As shown in Figure 7, with the normal direction on the plane of base material 100 as direction D3.
Incident comprises the incident light of rectilinearly polarized light in this sensor chip.The direction of polarized light of rectilinearly polarized light (polarized light orientation) is with respect to the parallel direction with the direction D1 face parallel with direction D3.This incident light is to metal grating 150 incident obliquely that is made up of the metallic film 140 and the first projection crowd 110.Specifically, when with the pitch angle during as θ, θ＞0 then, in cross section shown in Figure 7, the angle between the reverse direction of incident direction and direction D3 (with respect to the angle towards the vertical line on the plane of base material 100) makes incident light incident for the mode of θ.
In addition; In above-mentioned, though to rectilinearly polarized light with respect to being illustrated, in the present embodiment with the direction D1 parallel situation of face parallel with direction D3; Rectilinearly polarized light can be non-parallel with respect to above-mentioned also, as long as and comprise and above-mentioned parallel polarized light component.In addition, in above-mentioned, though be employed in the formation that has formed metallic film 140 on the glass substrate 130 as base material 100, present embodiment is not limited thereto.For example, the base material 100 of present embodiment also can form metallic film on quartz base plate or sapphire substrate.In addition, also can use the flat board that constitutes by metal as base material 100.
Fig. 8 illustrates the characteristic example of the intensity of reflected light of sensor chip.Fig. 8 is forming metal grating by Ag; Light is 3 degree with respect to the incident angle θ of metal grating, the groove direction D2 quadrature of polarisation of light light direction and metal grating, and the cross section of projection is rectangle (essentially rectangular); Cycle P1 is 500nm, the characteristic example when height H 1 is 20nm.In addition, transverse axis is represented catoptrical wavelength, and the longitudinal axis is represented intensity of reflected light (with respect to the ratio of incident intensity).
As shown in Figure 8, there are two surface plasmon polariton (SPP:Surface Plasmon Polariton: resonance peak surface plasmons) in the metal grating of present embodiment.For example, a resonance peak is positioned near the wavelength 515nm, and another resonance peak is positioned near the wavelength 555nm.Through making these two resonance peaks, thereby can expect bigger enhancing Raman scattering effect near coincidence (perhaps consistent) excitation wavelength and the Raman scattering wavelength.For example, when the argon laser with wavelength 515nm was used as excitation wavelength, (Raman shift 1200 was to 1600cm can to make near the Raman diffused light of wavelength 555nm
-1) strengthen strongly.
In addition, as the object that present embodiment was suitable for, such as pathogen such as rare molecule such as imaginary Poison, alcohol and remains of pesticide, viruses.
4. the establishing method of resonance peak wavelength
With reference to Fig. 9, the establishing method of two resonance peak wavelength is described.At first, the function to the sensor chip of present embodiment describes.
When the grating face of light incident sensor chip, through the concavo-convex generation surface plasma of grating.In the present embodiment, with respect to the grating face of sensor chip from the vergence direction incident light.This incident angle θ is (for example 10 degree below) several times.When making the groove direction quadrature of polarization of incident light light direction and grating,, excite electromagnetic vibration along with the vibration of the free electron in the metal grating.Because the vibration of this electromagnetic vibration effect free electron, so form the system that both vibrate that has been coupled, be surface plasmon polariton.
This surface plasmon polariton is propagated along the surface of sensor chip.Specifically, surface plasmon polariton is propagated along the interface between air and the metal grating, and near metal grating, excites stronger local electric field.The coupling of surface plasmon polariton is responsive to light wavelength, and its coupling efficiency is high.And, when grating surface such as being adsorbed with one during to several objects, SERS will take place therefrom.Like this, excite the enhancing electric field through surface plasmon polariton, thereby and manifest SERS through the interaction that strengthens electric field and object by incident light as the air borne pattern.In the present embodiment, can make the narrowed width of intensity of reflected light spectrum, make two resonance peaks sharp-pointed.Through like this, can realize improving transducer sensitivity, and realization can be according to the sensor chip of SERS spectrum intended target thing.
Fig. 9 illustrates the key diagram of the shooting conditions of surface plasmon polariton.The dispersion plot of C1 presentation surface plasmon polariton shown in Figure 9 (for example, the dispersion plot on the boundary surface of air and Au), C2 representes light.In Fig. 9, with cycle of metal grating as P1, the wave number 2 π/P1 of grating vector at this moment is shown on transverse axis.
At first, the relation between metal grating and the shooting conditions is described.When with the wave number of incident light as ki, with incident angle during as θ, the orientation of metal grating (direction D1 shown in Figure 7 or-wave number of D1) an evanescent wave (evanescent wave) is 2 π/P1 ± kisin θ.Surface plasmon polariton is excited when the wave number of the wave number 2 π/P1 ± kisin θ of this evanescent wave and surface plasma is consistent.That is to say that the shooting conditions of surface plasmon polariton is represented through the intersection point between the dispersion plot of straight line and the surface plasmon polariton of the formation condition of expression evanescent wave.
The C3 of Fig. 9 illustrates the comparative example as present embodiment, is illustrated in the straight line of the formation condition of the evanescent wave when the vertical incident light (θ=0) of metal grating.Shown in the C3 of Fig. 9, the wave number of evanescent wave is at this moment represented with 2 π/P1.This straight line C3 is the line that upwards prolongs from the beam location of grating vector, and intersects with the dispersion plot C1 of surface plasmon polariton.At this moment, intersection point is one, and a frequencies omega 0 (angular frequency) only appears in resonance peak.
C4 and C5 illustrate the straight line of the formation condition of expression evanescent wave in the present embodiment.When to the light resemble the present embodiment during with angle θ (θ＞0) incident metal grating, the wave number of evanescent wave is represented with 2 π/P1 ± kisin θ.Straight line C4 is corresponding with 2 π/P1+kisin θ, and straight line C5 is corresponding with 2 π/P1-kisin θ.These straight line C4 and straight line C5 are the lines that prolongs to oblique upper with angle θ from the position of the wave number of grating vector, and intersect at 2 with the dispersion plot C1 of surface plasmon polariton.Therefore, resonance peak frequency of occurrences ω+and these two of frequencies omega-(corresponding with wavelength X p1 and wavelength X p2 respectively).
In the present embodiment, utilize the shooting conditions of above-mentioned surface plasmon polariton, set two resonance peak wavelength X p1 and wavelength X p2, and these two resonance peak wavelength are used for SERS.Specifically, at first, obtain dispersion plot C1 (L.Li and C.W.Haggans J.Opt.Soc.Am., A10,1184-1189 (1993)) through rigorous couple-wave analysis (RCWA:Rigorous Coupled Wave Analysis, rigorous couple-wave analysis).Dispersion plot C1 is an intrinsic curve in the cross sectional shape of metal species, medium class, metal grating.Then, the grating cycle P1 and the incident angle θ that expect according to the Raman shift decision of object.That is to say, with the first resonance peak wavelength X p1 be set in excitation wavelength (Rayleigh scattering wavelength) near, with the second resonance peak wavelength X p2 (λ p2＞λ p1) be set in the Raman scattering wavelength near.And with the intersection point of straight line C4 through dispersion plot C1 and ω=ω+(λ=λ p1), straight line C5 sets grating cycle P1 and incident angle θ through the mode of the intersection point of dispersion plot C1 and ω=ω-(λ=λ p2).
Like this, the incident angle θ of material that can be through setting metal grating or shape, height H 1, grating cycle P1, light, thereby the value of setting the wavelength X p1 and the wavelength X p2 of two resonance peaks for expection.
So,, when surface plasma body resonant vibration only has the resonance peak of a broadness, have and be difficult in the whole process of SERS, obtain the problem of sufficient electric filed enhanced effect as described in the above-mentioned comparative example.
About this point, as shown in Figure 7, the optical device of present embodiment has the first projection crowd 110, and this first projection crowd arranges with period 1 P1 through the direction D1 that the projection edge of electric conductor is parallel with the plane of base material 100 (sensu lato imaginary plane).Go into the light (wavelength X, incident angle θ) that direction that directive tilts with respect to the vertical line towards the plane of base material 100 is advanced the first projection crowd 110 who arranges with this period 1 P1.As shown in Figure 9, through this incident light, in the first resonance peak wavelength X p1 and the second resonance peak wavelength X p2, produce surface plasma body resonant vibration respectively.At this moment, as shown in Figure 8, the first resonance peak wave band BW1 that comprises the first resonance peak wavelength X p1 comprises the excitation wavelength lambda 1 in the SERS.The second resonance peak wave band BW2 that comprises the second resonance peak λ p2 comprises the Raman scattering wavelength X 2 in the SERS.
Here, the width of wave band BW1, BW2 be exactly the regulation intensity of reflected light in the section wide, such as the half width that is peak value.In addition, in Fig. 8, though be regarded as λ 1=λ p1, λ 2=λ p2, in the present embodiment, λ 1 and λ p1 also can be different, and λ 2 and λ p2 also can be different.In addition, so-called imaginary plane is meant that with incident angle of the first projection crowd's 110 orientation, incident light etc. be the plane of benchmark, such as being the parallel face in plane (the for example surface 120 of base material 100) with base material 100.
According to the foregoing description, can in the whole process of SERS, improve the electric field enhancing degree.That is to say; Through comprise the mode of wavelength X 1, wavelength X 2 with two resonance peak wave band BW1, BW2; Setting cycle P1, incident angle θ etc., thus electric field enhancing degree and the electric field enhancing degree in the Raman scattering wavelength X 2 in the excitation wavelength lambda 1 can be improved.
In addition, according to the foregoing description, the incident angle θ of material through suitable change metal grating or cross sectional shape, cycle P1, height H 1, light, thus can make the position of two resonance peaks consistent with arbitrary value with at interval.Therefore, the light wavelength λ in that shines in the time of can suitably being chosen in the intended target thing, and can expand the width of measuring wavelength coverage.
In addition, in the present embodiment, Raman scattering wavelength X 2 is to be longer than the wavelength of excitation wavelength lambda 1 (λ 2＞λ 1).
In view of the above, can in the Stokes composition and anti-Stokes composition of Raman diffused light, measure the bigger Stokes composition of scattering strength.In addition, in the present embodiment, also can use the anti-Stokes composition of λ 2＜λ 1.
In addition; In the present embodiment; As shown in Figure 7; Incident has rectilinearly polarized light as incident light, and on the direction of polarized light of this rectilinearly polarized light and parallel plane composition base material 100 (with respect to the rectangular projection on the plane of the base material on the direction of polarized light 100) and the first projection crowd's 110 orientation D1 parallel.
In view of the above, the dilatational wave through rectilinearly polarized light free electron plasma is to the direction inductor along direction D1, thereby can excite the surface plasma of propagating along the first projection crowd's 110 orientation D1.
In addition, in the present embodiment,, on the first projection crowd's 110 end face 220, also can comprise the second projection crowd 200 who forms by metal as stating after carrying out among Figure 12 etc.And the second projection crowd 200 also can the edge and the parallel plane direction D1 of base material 100, with the second round P2 shorter than period 1 P1 (P2＜P1) arrange.
In addition; In the present embodiment; As stating after carrying out among Figure 12 etc., also can comprise the 3rd projection crowd 210 who forms by metal being arranged with the first projection crowd 110 and being positioned on the face 230 (bottom surface 230 between the first projection crowd's 110 abutment lug) between the first projection crowd's 110 abutment lug.And, the 3rd projection crowd 210 also can along with the parallel plane direction D1 of base material 100, with the period 3 P3 shorter (P3＜P1) arrange than said period 1 P1.
In view of the above, excite the propagation surface plasma, on the second projection crowd 200 and the 3rd projection crowd 210, excite local surface plasma through this propagation surface plasma through the first projection crowd 110.Through like this, can further improve the electric field enhancing degree in excitation wavelength and the Raman scattering wavelength.
5. variation
In above-mentioned Fig. 8,, in the present embodiment, also can form metal grating 150 by Au though the situation that is formed metal grating 150 by Ag is illustrated.Figure 10 illustrates the characteristic example of the intensity of reflected light of sensor chip at this moment.Figure 10 is to be 5 degree at light with respect to the incident angle θ of metal grating, the groove quadrature of polarisation of light light direction and metal grating, and the cross section of projection is rectangle (essentially rectangular), and cycle P1 is 500nm, and the characteristic when height H 1 is 40nm is routine.
Shown in figure 10, a peak value in two resonance peaks is positioned at wavelength 545nm, and another peak value is positioned at wavelength 600nm.Through making near this two resonance peaks coincidence excitation wavelength and Raman scattering wavelength, thereby can obtain the signal of stronger SERS.
In the metal grating that forms by this Au, to compare with the metal grating that forms by Ag shown in Figure 8, the wavelength of two resonance peaks is different, and resonance peak is wide slightly, and resonance peak shoals.But, compare with the situation of only utilizing a resonance peak, it is remarkable extraordinarily that enhanced surface strengthens the effect of Raman scattering signal.In addition, through using Au, thereby can suppress the surface deterioration that causes because of oxidation or sulfuration etc.In addition, as shown in Figure 8, when using Ag, to compare with Au, resonance peak is narrow dark.Therefore, compare, can further improve the reinforced effects of the signal of SERS with Au.
Here; In above embodiment; Though used and had Ag or the Au that makes the rerum natura that surface plasma, surface plasmon polariton or SERS manifest strongly; But in the present embodiment, in addition, also can adopt Pt (platinum), Cu (copper) or Al metals such as (aluminium).
6. second constitutes example
In the above-described embodiments, though excite the propagation surface plasma through the first projection crowd 110, in the present embodiment, diffraction grating also can comprise other projections crowd (metal micro structure) who excites local surface plasma.With reference to Figure 11 and Figure 12, second of such sensor chip is constituted example describe.
Figure 11 is the stereographic map that second of sensor chip constitutes example.This sensor chip comprises base material 100, the first projection crowd 110, the second projection crowd 200 and the 3rd projection crowd 210.In addition, below, to the additional same-sign of the inscape identical, and suitably omit explanation with the inscape of in Fig. 7 etc., having explained.
Shown in figure 11, the first projection crowd, 110 edges dispose with the parallel plane first direction D1 of base material 100 periodically.And the second projection crowd 200 disposes at the first projection crowd's 110 end face 220 upper edge direction D1 periodically.Bottom surface 230 (plane of base material 100) the upper edge direction D1 of the 3rd projection crowd 210 between the first projection crowd's 110 projection disposes periodically.
More particularly, the second projection crowd 200 and the 3rd projection crowd's 210 the cross sectional shape of each projection on the orientation D1 of projection forms convex form from end face 220 and bottom surface 230.Convex form is rectangle, trapezoidal or arc etc.For example, shown in figure 11, when overlooking base material 100, the second projection crowd 200 forms the striated parallel with direction D2 with the 3rd projection crowd 210.This second projection crowd 200 and the 3rd projection crowd 210 both can be by having formed with the first projection crowd, 110 identical metals, also can be by forming with its different metallic.
Figure 12 illustrates the sectional view of the sensor chip of the second formation example.The cross section of this sectional view is the face vertical with the plane of base material 100, and it is the face parallel with direction D1.Shown in figure 12, the second projection crowd 200 is H2 apart from the height of end face 220, and it is arranged with the cycle P2 shorter than cycle P1.The 3rd projection crowd 210 is H3 apart from the height of bottom surface 230, and it is arranged with the cycle P3 shorter than cycle P1.Be preferably set to smaller or equal to 500nm such as cycle P2, cycle P3, height H 2, height H 3 are preferably set to smaller or equal to 200nm.In addition, height H 3 both can be H3＞H1, can be H3≤H1 again.
Here; In above-mentioned; Though the second projection crowd 200 and the 3rd projection crowd's 210 the orientation situation for the orientation D1 identical with the first projection crowd 110 is illustrated; But in the present embodiment, the second projection crowd 200 and the 3rd projection crowd's 210 orientation also can be the direction different with D1.At this moment, arrangement cycle P2, arrangement cycle P3 become the arrangement cycle in direction D1.
Then, the SERS to the routine sensor chip of this second formation describes.In the present embodiment, make exciting light be incident to sensor chip obliquely with angle θ.Like this, as stated,, in excitation wavelength (Rayleigh scattering wavelength) and Raman scattering wavelength, excite propagation surface plasma with two resonance peaks through the first projection crowd 110.This surface plasma is propagated along the surface of metal grating 150, and in the second projection crowd 200 and the 3rd projection crowd 210, excites local surface plasma.And this local surface plasma excites the enhancing electric field between the second projection crowd 200 and the 3rd projection crowd's 210 projection, strengthens the interaction of electric field and object through this, produces SERS.At this moment, because the second projection crowd 200 and the 3rd projection crowd's 210 projection is narrow at interval, so between projection, excite stronger enhancing electric field.Therefore, though the object of sorption between projection be one to several, also can strengthen electric field and produce stronger SERS through this.
7. analytical equipment
Figure 13 illustrates the formation example of the analytical equipment of the sensor chip that comprises present embodiment.This analytical equipment (sensu lato spectroscopy equipment) comprises sensor chip 300 (optical device), light source 310, collimation lens 320, polarized light control element 330, object lens 350 (first optical system), dichronic mirror 340, collector lens 360, etalon (etalon) 370 (in a broad sense, dichronic mirror 340, collector lens 360 and etalon 370 constitute second optical system), photodetector 380 (detecting device) and delivery section 420.In addition, the analytical equipment of present embodiment is not limited to the formation of Figure 13, can omit the part (for example delivery section) of its inscape or append the various distortion of other inscape etc.
Light source 310 penetrates the laser light of excitating surface plasma polariton and SERS.The light of the laser that penetrates from light source 310 becomes directional light through collimation lens 320, and becomes rectilinearly polarized light through polarized light control element 330.Laser light through polarized light control element 330 is directed to the direction of sensor chip 300 through dichronic mirror 340, and passes through object lens 350 optically focused, thus incident sensor chip 300.On the surface of sensor chip 300, be formed with such as metal grating or detection material selection mechanism.The period ratio laser light wavelength of this metal grating is short.
Arrow shown in Figure 8 illustrates the throughput direction of object.Object is through the driving of control fan (not shown), from the input port 400 import delivery section 420 inside, and be discharged to the outside of delivery section 420 from escape hole 410.At this moment, the part of the object through delivery section 420 is attached on the sensor chip 300 that is supported by support portion 430, thereby on the surface of sensor chip 300, disposes object (not shown).
When to the light time of metal grating surface incident laser, along with the vibration of the light of laser, free electron resonance, and near the metal grating surface, produce through surface plasmon polariton extremely strong enhancing electric field is arranged.When strengthen for example one during to several target substance, of invasion in electric field at this from producing SERS here.Rayleigh scattering light and Raman diffused light from sensor chip 300 pass through object lens 350, by the direction of dichronic mirror 340 direct light detecting devices 380.This scattered light passes through collector lens 360 optically focused, and through etalon 370 (optical splitter), incident light detecting device 380.And, from scattered light beam split Raman diffused light, and receive (receiving light) these Raman diffused lights through etalon 370 through photodetector 380.Like this, scattered light is by spectral resolution, and can obtain the spectral information of object.
According to above analytical equipment, through having the sensor chip 300, thereby can produce SERS, and this Raman diffused light of beam split selectively, and can detect object.Through like this, can realize improving the sensitivity of sensor, and can be according to SERS spectrum intended target thing.
In addition, the analytical equipment of present embodiment can be widely used in detection, medical treatment and the Gernral Check-up of drugs and explosive, the employed sensing detection device of inspection of food.In addition, can wait and use as the affinity sensor (affinity sensor) that has or not material absorption having or not of the absorption that detects the antigen in antigen-antibody reaction etc.
Figure 14 illustrates and is used to make the key diagram of incident light oblique incidence to first method of sensor chip.In this first method,, incident beam Lin is tilted with respect to sensor chip 300 through departing from the optical axis incident incident beam Lin (incident light) of object lens 350.
Specifically, the optical axis of sensor chip 300 with object lens 350 is located vertically on the support portion 430.And, only from the optical axis predetermined distance of object lens 350, and with the optical axis of object lens 350 incident incident beam Lin abreast.Predetermined distance is the incident angle of incident beam Lin incident sensor chip 300 becomes the θ angle through the refraction of object lens 350 a distance.From scattered light Lsc (perhaps reflected light) the incident object lens 350 of sensor chip 300, and the optical system of the back level through object lens 350 guiding dichronic mirrors 340 etc.
Figure 15 illustrates the key diagram that is used for to second method of sensor chip oblique incidence incident light.In this second method; Through making the optical axis incident as one man of incident beam Lin (incident light) and object lens 350; Optical axis with respect to object lens 350 disposes sensor chip 300 obliquely on the other hand, thereby incident beam Lin is tilted with respect to sensor chip 300.
Specifically, the normal on the plane (plane of base material 100) of sensor chip 300 and the optical axis angulation of object lens 350 are configured to θ.And, make the optical axis incident of incident beam Lin along object lens 350.Like this, incident beam Lin is not reflected through object lens 350, and with incident angle θ incident sensor chip 300.Scattered light Lsc and above-mentioned first method from sensor chip 300 are same, are directed to the optical system of back level through object lens 350.In addition, in the present embodiment, tilt in order to make sensor chip 300, shown in figure 15, support portion 430 was tilted, again can be with the supporting surface of support portion 430 as the dip plane.
In addition, though embodiments of the invention have been carried out explanation at length, as long as not breaking away from inventive point of the present invention and effect in fact can have a lot of distortion, this will be readily apparent to persons skilled in the art.Therefore, such variation also all is included within protection scope of the present invention.For example; In instructions or accompanying drawing; Have once the term of putting down in writing simultaneously with different terms of broad sense or meaning (object, incident light, diffraction grating, electric conductor etc.) more (target substance, exciting light, metal grating, metal etc.) at least, can replace to the broad sense term different Anywhere with meaning at instructions or accompanying drawing.In addition, the formation of optical device, analytical equipment etc., also to be not limited to present embodiment illustrated in action, and various distortion can be arranged.
Symbol description
10 transparency carriers, 20 metal particles
100 base materials, 110 first projection crowds
140 metallic films, 150 metal gratings
200 second projection crowds 210 the 3rd projection crowd
220 first projection crowds' end face
Bottom surface between 230 first projection crowds' abutment lug
300 sensor chips, 310 light sources
320 collimation lenses, 330 polarized light control elements
340 dichronic mirrors, 350 object lens
360 collector lenses, 370 etalons
380 photodetectors, 400 input ports
410 escape holes, 420 delivery section
The BW1 first resonance peak wave band BW2 second resonance peak wave band
D1 first direction Lin incident light
The Lsc scattered light P1 period 1
The P2 P3 second round period 3
Ram Raman diffused light Ray Rayleigh scattering light
X target molecule θ incident angle
The wavelength X p1 first resonance peak wavelength of λ in incident light
The λ p2 second resonance peak wavelength ω+, ω-resonant frequency
Claims (9)
1. an optical device is characterized in that,
Said optical device has: the first projection crowd, the said first projection crowd arrange with the period 1 through the direction that the projection edge of electric conductor is parallel with imaginary plane and form,
Wherein, produce at the first resonance peak wavelength and the second resonance peak wavelength respectively at the surface plasma body resonant vibration that makes light be incident to the said first projection group time, the said light that only advances along the direction that tilts with respect to vertical line towards said imaginary plane,
The first resonance peak wave band that comprises the said first resonance peak wavelength comprises the excitation wavelength lambda 1 in the SERS,
The second resonance peak wave band that comprises the said second resonance peak wavelength comprises the Raman scattering wavelength X 2 in the said SERS.
2. optical device according to claim 1 is characterized in that,
Said Raman scattering wavelength X 2 is to be longer than the wavelength of said excitation wavelength lambda 1.
3. optical device according to claim 1 and 2 is characterized in that,
As said incident light incident rectilinearly polarized light is arranged, composition parallel with said imaginary plane on the polarization direction of said rectilinearly polarized light and the said first projection crowd's orientation parallel.
4. according to each described optical device in the claim 1 to 3, it is characterized in that,
End face the said first projection crowd comprises the second projection crowd who is formed by electric conductor,
The said second projection crowd edge direction parallel with said imaginary plane is to arrange the second round that is shorter than the said period 1.
5. according to each described optical device in the claim 1 to 4, it is characterized in that,
Comprise the 3rd projection crowd who forms by electric conductor at the face that is arranged with the said first projection crowd and be positioned between the said first projection crowd's abutment lug,
Said the 3rd projection crowd edge direction parallel with said imaginary plane arranged with the period 3 that is shorter than the said period 1.
6. an analytical equipment is characterized in that, comprising:
Light source;
According to each described optical device in the claim 1 to 5;
First optical system makes from the incident light of the said wavelength X 1 of said light source to tilt with respect to the vertical line towards the said imaginary plane of said optical device and be incident to said electric conductor grating;
Second optical system is extracted Raman diffused light from the light of said electric conductor grating scattering through said optical device or reflection; And
Detecting device detects the said Raman diffused light that receives through said second optical system.
7. analytical equipment according to claim 6 is characterized in that,
Said first optical system departs from the optical axis ground incident of said first optical system through making said incident light, thereby makes said incident light with respect to tilting towards the vertical line of said imaginary plane and being incident to said electric conductor grating.
8. analytical equipment according to claim 6 is characterized in that,
Said analytical equipment also comprises: the support portion, and make towards the vertical line of the said imaginary plane of said optical device inclined light shaft, and support said optical device with respect to said first optical system,
Said first optical system is through making said incident light with the mode incident consistent with the optical axis of said first optical system, thereby said incident light is tilted with respect to the vertical line towards said imaginary plane and is incident to said electric conductor grating.
9. a light-splitting method is characterized in that, comprising:
Prepare the first projection crowd, the said first projection crowd arranges with the period 1 through the direction that the projection edge of electric conductor is parallel with imaginary plane and forms;
Make light be incident to the said first projection crowd, the said light that only advances along the direction that tilts with respect to vertical line towards said imaginary plane; And
Produce surface plasma body resonant vibration at the first resonance peak wavelength and the second resonance peak wavelength respectively,
Wherein, the first resonance peak wave band that comprises the said first resonance peak wavelength comprises the excitation wavelength lambda 1 in the SERS,
The second resonance peak wave band that comprises the said second resonance peak wavelength comprises the Raman scattering wavelength X 2 in the said SERS.
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| JP2010-103035 | 2010-04-28 | ||
| JP2010103035A JP5609241B2 (en) | 2010-04-28 | 2010-04-28 | Spectroscopic method and analyzer |
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| US (1) | US8848182B2 (en) |
| EP (1) | EP2383565A1 (en) |
| JP (1) | JP5609241B2 (en) |
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Also Published As
| Publication number | Publication date |
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| JP5609241B2 (en) | 2014-10-22 |
| EP2383565A1 (en) | 2011-11-02 |
| JP2011232186A (en) | 2011-11-17 |
| US8848182B2 (en) | 2014-09-30 |
| TWI567375B (en) | 2017-01-21 |
| KR20110120233A (en) | 2011-11-03 |
| CN102608823B (en) | 2016-02-03 |
| TW201213791A (en) | 2012-04-01 |
| US20110267613A1 (en) | 2011-11-03 |
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